Controlling viscosity of synthetic detergent-soap shampoos



United States Patent O 3,001,944 CONTROLLING VISCOSITY F SYNTHETIC DETERGENT-SOAP SHAMPOGS Ling Wei, North Bergen, N..I., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware N0 Drawing. Filed July 12, 1957, Ser. No. 671,414

2 Claims. (Cl. 252-117) This invention relates to a new process for regulating the viscosity of aqueous washing products and to the resulting compositions. More particularly, it is of a process of thinning shampoos containing anionic synthetic detergents and soap by the addition of particular polyoxyalkylene compounds, and the product obtained from the process.

Shampoos containing both anionic synthetic detergent and soap are useful cleansing agents for human hair. This is especially true where hard water limits the utility of pure soap shampoos. The metallic ions which contribute to water hardness precepitate soap at the low concentrations occurring during the rinsing operation, causing lime soap to deposit on the hair filaments. This coating of grayish insoluble soap dulls the appearance of the hair and prevents attainment of the lustre indicative of cleanliness. The synthetic detergents in the present synthetic detergent-soap shampoos complement the cleaning ability of the soap and, additionally, often help to prevent the precipitation of insoluble soaps by hard water, facilitating the obtention of clean lustrous hair without the necessity of employing an acid rinse to destroy deposited insoluble soap.

In manufacturing anionic synthetic detergent-soap shampoos it has been found that the viscosity of the finished products is variable. Thus, even though the same formula is used and the ingredients, for usual purposes, appear to be the same, it has often been found that the products obtained are often of noticeably different viscosities.

In any cosmetic preparation it is of the greatest importance that there be no observable difference between batches of the same formula sold under one trade identification because the consumer considers uniformity to be a primary indication of quality. Therefore, to make a commercially acceptable anionic synthetic detergent-soap shampoo one must regulate the viscosity of the end product. One way to do this is by formulating so that all finished products are above the desired viscosity and then adding a thinning agent to lower the viscosity to the required value.

In accordance with the present invention a process for reducing the viscosity of an anionic synthetic detergent-soap shampoo comprises adding to such a shampoo an amount between 0.01 and 2.0 percent of an aliphatic polyoxyalkylene compound of the formula R (OC I-I OR wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon radicals, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n, the average number of carbon atoms in the lower monoxyalkylene monomeric constitucuts of the chain, is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 400 in which the sum of R and R comprises up to percent of the molecular weight. Of course, this method is generally useful for thinning anionic synthetic detergent-soap shampoos when so desired, in addition to allowing the production of such shampoos of controlled viscosity from batch to batch.

The synthetic detergent component of the present shampoos may be any of anionic character, of the same general ionic structure as soap, compatible therewith, stable, readily available and of good cleaning and lime soap dispersing properties. Cationic detergents are not employed because, with few exceptions, they are incompatible with soap and other anionic detergents. Certain nonionic detergents may be used together with anionic synthetic detergents and soap but the final product should not contain more than the upper process limit, 2 percent, of the viscosity-lowering additive 'Ihe anionic detergents, examples of which are given below, are used in the form of their water soluble or emulsion-forming salts such as the amine, alkali metal and alkaline earth metal salts. The ammonium and amine salts (including alkylolamine salts) of these detergents are usually preferred when clear products are desired because of their generally greater solubility in aqueous media, but their sodium, potassium, magnesium salts and the like are also useful.

Among the suitable anionic compounds that may be used are the aliphatic sulfated or sulfonated detergents. Included in that group are acyl-containing compounds wherein the acyl radical has about 8 to 22 carbon atoms, and more particularly the aliphatic carboxylic ester type, containing 12 to 22 carbon atoms to the molecule. Suitable examples of these aliphatic detergents are the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, either saturated or unsaturated, particularly those whose acyl groups contain from 12 to 18 carbon atoms, e.g., coconut oil monoglyceride monosulfate, hydrogenated coconut oil monoglyceride monosulfate, tallow diglyceride monosulfate, lauroyl monoglyceride monosulfate; the long chain pure or mixed higher alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate, higher fatty alcohol sulfates derived from hydrogenated or non-hydrogenated coconut oil or tallow fatty acids; the higher fatty acid esters of hydroxy alkyl sulfonic acids; higher fatty acid amides of amino alkyl sulfonic acids, e.g., the oleic acid amide of amino methyl sulfonic acid, the lauric acid amide of taurine, and the like.

Other appropriate, aliphatic sulf(on)ates include fatty sulfoacetates, e.g., coconut fatty alcohol sulfoacetates; sulfated fatty acyl monoethanolamides, e.g., sulfated lauroyl monoethanolamide; fatty sulfoacetamides, e.g., lauryl sulfoacetamide; alkyl sulfosuccinates, e.g., dioctyl sulfo-succinate; sulf(on)ated fatty oils such as sulf(on)- ated caster oil and sulf(on)ated red oil.

In addition, the higher alkyl or acyl substituted amino acids, e.g., N-lauroyl sarcosine, are anionic detergents contemplated as ingredients of the composition of this invention. Also included are the alkylphenol polyglycol ether sulfates, e.g., the lauryl phenol polyglycol ether sulfates containing three moles ethylene oxide per mole.

The alkyl aryl sulfonates may also be used as the nonsoap anionic detergent although not usually preferred in shampoos because of their usually excessive drying power. Typical of this class of compounds are the higher alkyl aromatic sulfonates wherein the nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc. The number of sulfonic groups may vary but generally these compounds contain one such configuration only. The alkyl substituents may be branched or straight chain, such as decyl, dodecyl, keryl, hexadecyl, mixed long-chain alkyls derived from long-chain fatty materials, cracked parafiin wax olefins, polymers of lower mono-olefins, etc. Examples of the class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl group contains 8 to 22 carbon atoms, and preferably about 12 to 18.

The soaps that are constituents of the shampoos to be treated by the invented process include those commonly referred to by that appellation, namely the amine (including alltylolamine), ammonia and alkali metal salts of higher fatty acids of l-18 carbon atoms. The fatty acids may be unsaturated but sometimes it will be found advantageous to hydrogenate them. Usually soaps will be made from glycerides or mixtures of fatty acids, such as those obtained from coconut oil, palm kernel oil, soy bean oil, cottonseed oil and corn oil, which oils are pre ferred because soaps made from such comparatively low molecular weight higher fatty acids or unsaturated acids are usually quite soluble in aqueous and alcoholic media. These mixtures may contain small amounts of fatty acids, or the glyceride may be of fatty acids having a number of carbon atoms outside the 10-18 range. These soaps may contain small amounts of glycerine, inorganic salts, etc. They may also be made from fatty acids or mixtures thereof.

Examples of suitable fatty acyl components are the decanoic, lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acid radicals. Suitable soaps include triethanolamine oleate, sodium laurate and the sodium, potassium, amine and alkylolamine salts of coconut oil, soy bean oil, cottonseed oil and corn oil.

Mixtures of anionic synthetic detergents and/or mixtures of soaps may be used.

The aliphatic polyoxyalkylene compounds of formula R(OC H OR' are preferably water soluble but also include substances that form stable emulsions with the shampoo. In these compounds the (OC H OR' chain is made up of lower monoxyalkylene groups. By lower monoxyalkylene is meant a group containing no more than 6 carbon atoms. It should be noted that the average number of carbon atoms allowable, n, is from 2 to 3 so the amount of monoxyalkylene constituent of over 4 carbon atoms is necessarily minor. R and R' are either hydrogen or lower alkyl radicals, lower alkyl including radicals up to 6 carbon atoms.

Products of this type are prepared by condensing lower alkylene oxide with a compound containing an active hydrogen such as an alcohol or glycol. The average degree of alkoxylation or chain length can be regulated in the manufacturing process but due to the nature of this type of reaction the polyoxyalkylene will, in fact, normally be a mixture of groups in different polymerization stages. To be useful in the present invention the average molecular weight of the product must exceed 400 and the combined weights of R and R must be less than 10 percent of the said average molecular weight.

If the R(OC,,H ,,),,OR is composed of monoxyalkylene groups averaging more than 3 carbon atoms per group it loses its thinning power. This is also the tendency when the R and/or R groups are over 6 carbon atoms in length. In that case too, the rheological properties and viscosity are not stable on storage. Likewise, when the weight proportion of exceeds 1/10, the thinning power and shelf stability are not satisfactory. Below molecular weight 400 these compounds exert a known thinning effect, but the much greater amount that must be employed to secure equivalent viscosity reduction militates against their use.

As representative of the water soluble compounds may be mentioned the mono-lower alkyl ethers of poly-lower oxyalkylene glycol. These compounds are of the formula R(OC,,H OH. They will usually be very satisfactory if the monoxyalkylene groups contain no more than 4 carbon atoms, R contains from 1 to 6 carbon atoms, the average molecular weight of the compound is about LOGO-10,000 and R is up to percent of the molecular weight. The most preferred viscosity reducing agent is a mixture of aliphatic monohydroxy oxyethylene oxy 1,2-propylene butyl monoethers in which the weight ratio of oxyethylene to oxypropylene is from 2/3 to 3/2 and the average molecular weight is between 2,000 and 5,000. Processes for the manufacture of such products are found in US. Patent 2,424,755 granted to F. H. Roberts and H. R. Fife.

Water insoluble but emulsifiable analogues of the above products may be made by forming the diether where both R and R are alkyl radical and satisfy the same conditions as R above with the exception that the sum of R and R may equal 10 percent of the molecular weight. Where R equals H, as in the water soluble embodiments of the thinning agents of this invention R should be up to 5 percent of the molecular weight.

Another sub class of viscosity reducing agents of exceptionally high activity is the group of water soluble polyalkylene glycol block copolymers. These compounds are made by polymerizing lower alkylene oxide and/or glycol groups to form compounds containing separate hydrophobic and hydrophilic blocks or chains and having terminal hydroxy groups. To insure an excellent thinning action the average molecular weight of the product should be from 1,000 to 10,000 and the hydrophobic poly lower alkylene oxide chain has an average molecular weight of at least 800 and is located between the hydrophilic poly lower alkylene oxide chains which comprise 20-80 percent of the average molecule and terminate in hydroxyl. The preferred polymer of this sub-class is that which is a cogeneric mixture made from 1,2-propylene oxide (to form the central hydrophobic chain) and ethylene oxide (for the hydrophilic chains). In making these compounds a relatively small amount of propylene glycol may be employed initially to condense with propyl' ene oxide and give the hydrophobic chain terminal hydroxyls capable of reacting with ethylene oxide. For a more detailed description of a process of manufacture see Exgmple I of US. Patent 2,674,619, granted to L. G. Lunste An additional sub-class of materials which possess a remarkable thinning activity on anionic detergent-soap shampoos are the water soluble aliphatic lower 1,2-polyalkylene glycols of the formula H(OC H OH wherein m, the number of carbon atoms in the monoxy alkylene unit, is 2 and/or 3, and the molecular weight of which is between 400 and 10,000. The preferred embodiment of this sub-class is polyethylene glycol of molecular weight of 400 to 6,000.

Mixtures of the polyalkylene oxide compound thinning agents of the same or different sub-classes may be employed.

In addition to being utile in anionic synthetic detergentsoap shampoos it has been found that very small amounts, from 0.01 to 2.0 percent of the viscosity reducing agents of this invention, can thin synthetic detergents containing lower alkylolamide of higher fatty acids or alkylolamide mixtures. The fatty acid component of these alkylolamides has from 10-18 carbon atoms and the alkylol group has 2 or 3 carbon atoms. Preferably dialkylolamides are used. If a monoalkylolamide is employed it should have hydrogen or an alkyl group of 2 or 3 carbon atoms at the open nitrogen valence bond. As example of the preferred diethanolamides may be mentioned lauric diethanolamide, a mixture of lauric and myristic diethanolamides and lauric diisopropanolamide.

Ordinary anionic synthetic detergent solutions are not thick unless soap or some other agent which increases viscosity has been added. Alkylolamides are often added to anionic synthetic detergents to increase or stabilize foam but they also raise viscosity. To decrease this resultant viscosity when so desired the. alkoxy compounds of this invention are very effective. They are doubly useful when soap is also present since they. act on both soapand alkylolamide-thickened shampoos.

The sum of anionic synthetic detergent and soap in the anionic synthetic detergent-soap shampoos to be treated by the method of this invention may be from 5 to 50 percent, preferably, from to 35 percent of the finished shampoo. Below 5 percent the shampoos usually are not sufficiently effective in cleaning the hair. Above 50 percent there are gelation and solubility problems and the solids content is too high to permit economic use of the product by the average consumer according to his or her usual method.

The ratio of anionic synthetic detergent to soap in these shampoos may vary widely, from 9:1 to 1:9. Outside this range the minor component has little eifect on the viscosity of the shampoo. Preferably, the above ratio will be between 4:1 and 1:4.

The amount of anionic synthetic detergent in shampoos containing alkylolamide may be from 5 to 50 percent, preferably between 10 and 35 percent. The alkylolamide content should be at least 1 percent but no more than 10 percent. Preferably, it is about 5 percent. When soap is present the proportions of anionic synthetic detergent to soap are the same as given in the paragraph immediately preceding and the soap is considered to be a replacement for part of the synthetic detergent.

The balance of the shampoos of this invention, exclusive of the polyalkylene oxide compound used for viscosity control, is mostly water. To promote clarity the water is often deionized. Lower alcohols, e.g., ethanol, isopropanol, may be incorporated to increase solubility of perfumes, colorants, etc. Perfumes, dyes, conditioning agents and other usual adjuvant materials may be employed for their known functions.

Repeated experiments wherein pure soaps are mixed with pure synthetic detergents in aqueous solution will yield products of somewhat different viscosity depending on variations 1n the soaps and detergents due to subtle differences iln the oils from which they are derived. This erratic behavior is even more the rule when commercial soaps and detergents, containing the usual impurities such as salts, free fatty acids and other ether soluble materials, are employed. There is an evident need for an inexpensive simple method of regulating the viscosity of such shampoos without changing their other properties.

The polyalkylene oxide compounds of this invention are possessed of the unusual property of exerting surprisingly great thinning properties on soap-anionic synthetic detergent shampoos, alkylolamide-anionic synthetic detergent shampoos and soap alkylolamide-synthetic detergent combinations thereof when used in very small quantities. This thinning effect is controllable and a shampoo of almost any desired viscosity can be obtained by the addition of 0.01-2.0 percent of the described polyalkylene oxide compound. Usually, and preferably up to 1.0 percent of the polyalkylene oxide will be sufficient to exert the necessary thinning action.

As small an amount as 0.01 percent of the specific polyalkylene oxide products will exert a noticeable thinning activity on many shampoos. More than 2 percent will tend to modify other characteristics of the shampoo treated in addition to viscosity. This is undesirable be cause one of the important purposes of the present process is to reduce viscosity only, while leaving the other properties of the shampoo relatively constant, so that the brand-identified shampoo resulting uniform from batch to batch, whether or not slightly different amounts of thinning agent or any at all need be added.

The invention is not dependent upon any specific ranges of viscosity of the shampoo, either before or after treatment. Usually the untreated shampoo will have been reduced to form 20 to 700 centipoises, as desired.

The polyalkylene oxide compound is preferably added to the finished shampoo. Usually it is added as a liquid but solids, aqueous or alcoholic solutions and equivalents, even emulsions, are also employed. It is also possible to add the thinning agent during production of' the shampoo provided that a preliminary test has been conducted to determine the amount needed to adjust the viscosity. In another process some of the thinning,

agent is incorporated during compounding, to reduce viscosity and promote easier mixing, and afterward a smaller amount is added to the finished product for line adjustment of viscosity. Usually, additions will be made at room temperature but the process is also operative at higher and lower temperatures.

The reason for the exceptionally high thinning activity of the class of polyalkylene oxide compounds employed in this invention is not completely understood. Apparently the polyalkylene oxide chains are the critical active constituents. But not all polyalkylene oxide compounds are effective. Those having monoxyalkylene constituents of chain lengths containing an average of over 3 carbon atoms do not possess the same viscosity-reducing ability. Those averaging less than 2 are not chain compounds. If the product has a molecular weight below 400 it seems to possess only a solvent effect, rather than a special thinning activity. Such compounds are useless because relatively large amounts are needed to obtain sufficient viscosity reduction.

When the molecular weight is over 400 it has been found that if the compound contains a hydrocarbon group or chain of more than about 6 carbon atoms the resulting shampoo tends to become unstable. Such groups include the aliphatic, aromatic and alicyclic. The presence of these hydrocarbon chains usually either inhibits thinning or tends to aflYect the shelf age characteristics of the polyalkylene oxide compound, causing an unsatisfactory change with time in the viscosity of the treated shampoo. A similar condition obtains when the sum of R and R exceeds 10 percent of the product molecular weight or R, in the cases where R is H, exceeds 5 percent.

The following examples illustrate the invention. parts are by weight.

All

EXAMPLE I A series of anionic synthetic detergent-soap shampoos was made of the following formula:

Part A Parts Coconut oil fatty acids diethanolamide (92 percent solids) 1 5.0 Perfume q.s,

Sodium lauryl sulfate (30 percent aqueous paste, contains about 6 percent inorganic salt on solids basis) 30.0

T riethanolamine higher alkyl benzene sulfonate (60 percent aqueous paste) 13.0 Potassium soap (20 percent aqueous solution) 3 12.5

Part B Water, deionized 38.4 Phosphate bufier salt 0.5 Preservative 0.2

Footnotes-See Example V.

equal weights of ethylene oxide and 1,2 propylene oxide in the polyalkylene oxide chain, made according to the process of US. Patent 2,424,755. The following results were obtained:

Amount of Final Vis- Initlal Viscosity of Shampoo Additive eosity or (centipoises at 80 F.) (weight shampoo percent) (centipoises at 80 F.)

The shampoos made were all stable at 500 centipoises :50 cp., the usual allowable variation, for at least six months, after which tests were discontinued. Similar products to which had been added higher alkyl ethers of poly-lower alkylene glycols soon were of unsatisfactory viscosity.

Addition of 1 part of the viscosity lowering agent of Example I decreased the viscosity of this shampoo from 630 centipoises to 200 centipoises.

EXAMPLE III Parts Oleic acid (Red Oil) 16.4 Sodium lauryl sulfate (30 percent aqueous paste) 7.8 Triethanolamine 8.8 Deionized water 67.0

Addition of 0.5 percent of the thinning agent of Example I reduces the viscosity irom 775 centipoises to 105 centipoises.

EXAMPLEIV Parts Sodium lauryl sulfate (30 percent aqueous paste)" 33.3 Coconut oil fatty acids diethanolamide 50 Potassium soap (20 percent aqueous solution) 12.5 Deionized water 49.2

Footnotes-See Example V.

The viscosity of this shampoo was brought down from 1270 centipoises to 80 centipoises by the addition of 0.5 percent of polyethylene glycol of average molecular weight 1500.

EXAMPLE V Parts Coconut oil fatty acids diethanolarnide 5.0

Triethanolamine higher alkyl benzene sulfonate (60% aqueous paste) 2 16.7

Potassium soap (20% aqueous solution) 3 12.5 Deionized water 65.8 100.0

Commercial condensation product of diethanolamlne and coconut oil fatty acids, sold by the E. F. Drew Co. under the name Compound 119N. This product has a pH about 9 and contains minor amounts of fatty acid, dlethanolamine, esters and other condensation lay-products.

2 Sold under the trade name Ultrawet 60L.

3 Made from fatty oil having an iodine number of 65 and a saponificatlon value of 225.

* Tergitol XC.

The viscosity depressant used in the treatment of this shampoo is a cogeneric mixture of water soluble poly alkylene glycol block copolymers of ethylene oxide and propylene oxide, the propylene oxide chain having an average molecular weight of about 1200 and being located between ethylene oxide chains terminating in hydroxyl groups, the polyoxyethylene groups averaging about 40 percent of the molecule and the total molecular weight being about 2,000, made according to the process described in U.S. Patent 2,674,619. The addition of 0.5 percent of this material changed the shampoo viscosity from 210 centipoises to 40 centipoises.

The above invention has been described in conjunction with illustrative examples thereof. It will be obvious to those skilled in the art who read this specification that other variations and modifications of the invention can be made and various equivalents substituted therein witl1- out departing from the principles disclosed or going outside the scope of the specification or purview of the claims.

What is claimed is:

l. A process for making an aqueous liquid shampoo which comprises admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 001 and 2.0% of an aliphatic polyoxyalkylene compound of the formula R(OC,,H OR wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon radicals of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups of up to 6 carbon atoms, n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 400 in which the sum of R and R comprises up to 10 percent of the molecular weight, to reduce the viscosity of the soap-synthetic detergent shampoo.

2. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a water soluble aliphatic polyoxyalkylone compound of the formula R(OC H OH wherein R is a lower aliphatic hydrocarbon radical of l-6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene radicals of 24 carbon atoms, n, the average number of carbon atoms in the lower monoxyalkylene constituents of the chain, is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of about 1,000-10,000 in which R comprises up to 5 percent of the molecular weight, to reduce the viscosity of the soap-synthetic detergent shampoo.

3. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a water soluble mixture of aliphatic monohydroxy oxyethylene oxy 1,2-propylene butyl monoethers in which the weight ratio of oxyethylene to oxypropylene is from 2/3 to 3/2 and the average molecular weight is between 2,000 and 5,000, to reduce the viscosity of the soap-synthetic detergent shampoo.

4. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cationis selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a water soluble polyalkylene glycol block copolymer of a hydrophobic poly lower alkylene oxide chain of molecular weight at least 800 located between hydrophilic' poly lower alkylene' oxide chains terminating in hydroxyl groups, the lower alkylene oxides having up to 6 carbon atoms, the hydrophilic polyalkylene oxide groups comprising 20-80 percent of the molecule and the average molecular weights of the block copolymers being from 1000 to 10,000, to reduce the viscosity of the soap synthetic detergent shampoo.

5. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a cogeneric mixture of water soluble polyalkylene glycol block copolymers of propylene oxide chain having an average molecular weight of at least 800 and being located between ethylene oxide chains terminating in hydroxyl groups, the polyoxyethylene groups averaging 20-80 percent of the molecule and the average total molecular weight of the block copolymers being from 1000 to 10,000, to reduce the viscosity of the soap synthetic detergent shampoo.

*6. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolarnine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a water soluble aliphatic 1,2-polyalkylene glycol of the formula H(OC H OH wherein m is 2 to 3 and x is such as to give a product of molecular weight between 400 and 10,000, to reduce the viscosity of the soap-synthetic detergent shampoo.

7. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 110 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a non-soap anionic synthetic organic detergent in an aqueous liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired and admixing with such shampoo between 0.01 and 1% of a water soluble aliphatic lower polyethylene glycol of molecular weight of 400 to 6,000, to reduce the viscosity of the soap-synthetic detergent shampoo.

8. -A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid amide of a lower alkylolamine, the higher fatty acid being of 10 to '18 carbon atoms and the alkylolamine being selected from the group consisting of dialkylolamines in which the alkylol groups are of :2 to 3 carbon atoms and monoalkylolamines in which the alkylol group is of 2 to 3 carbon atoms and the nitrogen also has joined to it a substituent selected from the group consisting of hydrogen and lower alkyl groups of 2 to 3 carbon atoms, and a non-soap anionic synthetic organic detergent in a liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired, and admixing with such shampoo between 0.01 and 2.0 percent of a water soluble aliphatic polyoxyalkylene compound of the formula R(OC H OR wherein R and R are selected from the group consisting of hydrogen and lower aliphatic uct of average molecular weight of at least about 400 which the sum of R and R comprises up to 10 percent of the molecular Weight to reduce the viscosity of the alkylolamide-synthetic detergent shampoo.

9. A process for making an aqueous liquid shampoo comprising admixing a higher fatty acid soap of 10 to 18 carbon atoms in which the soap-forming cation is selected from the group consisting of sodium, potassium and triethanolamine, higher fatty acid amide of a lower alkylolamine, the higher fatty acid being of 10 to 18 carbon atoms and the lower alkylolamine being selected from the group consisting of dialkylolamines in which the alkylol groups are of 2 to 3 carbon atoms and monoalkylolamines in which the alkylol group is of 2 to 3 carbon atoms and the nitrogen also has joined to it a substituent selected from the group consisting of hydrogen and lower alkyl radicals of 2 to 3 carbon atoms, and a non-soap anionic synthetic organic detergent in a liquid medium, the shampoo composition thus prepared being of a viscosity higher than desired, and admixing with such shampoo between 0.01 and 1% of a water soluble aliphatic polyoxyalkylene compound-of the formula wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon radicals of up to 6 carbon atoms, (OC H Q is a polyoxyalkylene chain of lower monoxyalkylene groups of up to 6 carbon atoms, n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 400 in which the sum of R and R is up to 10 percent of the molecular weight, the amount of R(OC H OR' being sufiicient to lower the viscosity of the shampoo to the desired level.

10. An aqueous liquid shampoo comprising a soap of higher fatty acids of 10 to 18 carbon atoms in which the soap forming cation is selected from the group consisting of sodium, potassium and triethanolamine, and a nonsoap detergent selected from the group consisting of water soluble salts of sulfated and sulfonated synthetic organic anionic detergents, the ratio of soap to synthetic detergent being from 9:1 to 1:9, the total amount of soap and anionic synthetic organic detergent being 5 to 50% of the shampoo, and 0.01 to 1% of a soluble aliphatic polyoxyalkylene compound of the formula wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon radicals of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups of up to 6 carbon atoms, n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 400 in which the sum of R and R comprises up to 10% of the molecular weight and water.

11. An aqueous liquid champoo comprising a soap of higher fatty acids of 10 to 18 carbon atoms in which the soap forming cation is selected from the group consisting of sodium, potassium and triethanolamine, a non-soap detergent selected from the group consisting of water soluble salts of sulfated and sulfonated synthetic organic anionic detergents, the ratio of soap of synthetic detergent being from 9:1 to 1:9, the total amount of anionic synthetic organic detergent and soap being 5 to 50% of the shampoo, 1 to 10% of a dialkylolarnide of a higher fatty 1 1 acid of 10 to 18 carbon atoms and a lower dialkylolamine having alkylol groups of 2 to 3 carbon atoms, and 0.01 to 1% of a soluble aliphatic polyoxyalkylene compound of the formula R(OC,,H R

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon radicals of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups of up to 6 carbon atoms, 11, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 3, and x, the total number lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 400, in which the sum of R and R comprises up to 10% of the molecular weight and water.

12. An aqueous liquid shampoo comprising a soap of higher fatty acids of 10 to 18 carbon atoms in which the soap forming cation is selected from the group consisting of sodium, potassium and triethanolamine and a nonsoap detergent selected from the group consisting of water soluble salts of sulfated and sulfonated synthetic organic anionic detergents, the ratio of soap to synthetic organic detergent being from 9:1 to 1:9, the total amount of anionic synthetic organic detergent and soap being to 50% of the shampoo, and 0.01 to 1% of a soluble aliphatic polyoxyalkylene compound of the formula 12 wherein R is butyl, (OC H is a polyoxyalkylene chain of oxyethylene and oxy 1,2-propylene in which the ratio of oxyethylene to oxypropylene is from 2/3 to 3/2 and x is such as to give a product of average molecular weight between 2,000 and 5,000 and water.

References Cited, in the file of this patent UNITED STATES PATENTS QTHER REFERENCES Stupel: Manufacturing Chemist, March 1952, pp. 99- 102.

Information on Application of Pluronics, pp. 1, 4, 7, 11, pub. by Wyandotte Chemicals Corp., Wyandotte, Mich, Mar. 1, 1952.

Pluronics (a new series), pp. 3-9, publ. by Wyandotte Chemicals Corp., Wyandotte, Mich. (September 1954).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 OOI 944 September 26 196i Ling Wei It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 36 for "In" read in line 37 for "1121'" read in 3 line 711, for z'fiform readfrom a column 10 line 66 for shampoo, read shampoo line '12 for "soap oi read soap to Signed and sealed this 31st day of July 1962o (SEAL) Attest:

DAVID L. LADD ERNEST W SWIDER Attesting Officer Commissioner of Patents 

10. AN AQUEOUS LIQUID SHAMPOO COMPRISING A SOAP OF HIGHER FATTY ACIDS OF 10 TO 18 CARBON ATOMS IN WHICH THE SOAP FORMING CATION IS SELECTED FROM THE GROUP CONSISTING OF SOIDUM, POTASSIUM AND TRIETHANOLAMINE, AND A NONSOAP DETERGENT SELECTED FROM THE GROUP CONSISTING OF WATER SOLUBLE SALTS OF SULFATED AND SULFONATED SYNTHETIC ORGANIC ANIONIC DETERGENTS, THE RATIO OF SOAP TO SYNTHETIC DETERGENT BEING FROM 9:1 TO 1:9, THE TOTAL AMOUNT OF SOAP AND ANIONIC SYNTHETIC ORGANIC DETERGENT BEING 5 TO 50% OF THE SHAMPOO, AND 0.01 TO 1% OF SOLUBLE ALIPHATIC POLYOXYALKYLENE COMPOUND OF THE FORMULA 